Laundry detergent compositions comprising fabric enhancement polyamines

ABSTRACT

The present invention relates to laundry detergent compositions which can optionally comprise bleach, said compositions comprising a fabric enhancement system, said fabric enhancement system comprising one or more modified polyamine compounds.

This application claims priority under 35 USC 119(e) to provisionalapplication No. 60/120,993, filed Feb. 19, 1999.

FIELD OF THE INVENTION

The present application relates to laundry detergent compositions whichcomprise one or more crosslinked and/or grafted polyamines which provideenhanced fabric appearance benefits. The crosslinked and/or graftedpolyamines of the present invention which mitigate fabric damage andimprove fabric appearance are combined with detersive surfactants andoptionally a bleaching system for use in high and low density granular,heavy duty and light duty liquids, as well as laundry bar detergentcompositions.

BACKGROUND OF THE INVENTION

Formulators of fabric care and laundry detergent compositions includevarious ingredients, inter alia surfactants, cationic softening actives,anti-static agents, dye transfer inhibitors, and bleach-damagemitigating agents, for the purpose of improving cleaning, fabricappearance, fabric feel, fabric color and to extend the duration offabric life. Ingredients which are added to these compositions must notonly provide a benefit, but must be compatible with a variety of productforms, i.e. high density granules, liquid dispersions, isotropic liquidsincluding clear, colorless/translucent liquids which may includeprincipal solvents inter alia 1,2-hexanediol,2,2,4-trimethyl-1,3-pentanediol (TMPD).

There is a need for laundry detergent compositions which provide colorintegrity, as well as thoroughness of cleaning, which is considered bythe consumer to be an important aspect of fabric enhancement. Inaddition, there is a need for these protective materials to be highlywater soluble or water dispersible, while exhibiting a high degree offabric substantivity. And there is also a need for a fabric enhancementmaterial which will provide a high level of fabric protection on anefficient per unit weight basis.

SUMMARY OF THE INVENTION

The present invention meets the aforementioned needs in that it has beensurprisingly discovered that high molecular weight modified polyaminecompounds, preferably compounds formed by the reaction of grafted orungrafted and/or modified or unmodified polyamines with a crosslinkingagent wherein said modified polyamine compounds have a molecular weightof form about 1,000 daltons, preferably from about 10,000 daltons toabout 10 million daltons, preferably to about 2.5 million daltons, aresuitable for use in high and low density granular, heavy duty and lightduty liquids, as well as laundry bar detergent compositions to providefabric appearance benefits inter alia mitigation of fabric damage,prevention of fabric mechanical damage.

A first aspect of the present invention which relates to laundrydetergent compositions comprising:

a) from about 0.01% by weight, of a fabric enhancement system, saidfabric enhancement system comprising one or more modified polyaminecompounds, said modified polyamine compounds are selected from:

i) (PA)_(w)(T)_(x);

ii) (PA)_(w)(L)_(z);

iii) [(PA)_(w)(T)_(x)]_(y)[L]_(z); and

iv) mixtures thereof; wherein PA is a grafted or non-grafted, modifiedor unmodified polyamine backbone unit, T is an amide-formingpolycarboxylic acid crosslinking unit, and L is a non-amide formingcrosslinking unit; provided that for compounds of type (i) and (iii) theindices w and x have values such that the ratio of w to x is from 0.8:1to 1.5:1; for compounds of type (ii) the indices w and z have valuessuch that said modified polyamine compound comprises from about 0.05,preferably from about 0.3 to 2 parts by weight of said L unit; forcompounds of type (iii) the indices y and z have values such that saidmodified polyamine compound comprises from about 0.05, preferably fromabout 0.3 to 2 parts by weight of said L unit;

b) from about 0.01% by weight, of a detersive surfactant selected fromthe group consisting of anionic, cationic, nonionic, zwitterionic,ampholytic surfactants, and mixtures thereof; and

c) the balance carriers and adjunct ingredients.

These and other objects, features, and advantages will become apparentto those of ordinary skill in the art from a reading of the followingdetailed description and the appended claims. All percentages, ratiosand proportions herein are by weight, unless otherwise specified. Alltemperatures are in degrees Celsius (° C.) unless otherwise specified.All documents cited are in relevant part, incorporated herein byreference.

DETAILED DESCRIPTION OF THE INVENTION

The present invention relates to laundry detergent compositions whichcomprise a fabric enhancement system. The laundry detergent compositionscomprise from about 0.01%, preferably from about 0.1%, more preferablyfrom 0.25%, most preferably from about 0.5% to about 20%, preferably toabout 10%, more preferably to about 5% by weight, of a fabricenhancement system. Said fabric enhancement system is comprised of oneor more modified polyamine compounds. The fabric care and/or fabricenhancement compositions may take any form, for example, solids (i.e.,powders, granules, extrudates), gels, thixotropic liquids, liquids(i.e., dispersions, isotropic solutions), preferably the rinse-addedfabric conditioning compositions take the form of liquid dispersions orisotropic liquids.

For the purposes of the present invention the terms “fabric enhancement”and “fabric care” are used interchangeable throughout the presentspecification and stand equally well for one another. Fabricenhancement/fabric care is achieved when the properties inter aliacolor, fiber integrity of the garment are conserved (that is no furtherdamage is done during the laundry process) or the damaging process isreversed and the fabric appears more like its original form.

Fabric Enhancement System

The fabric enhancement system of the present invention is comprised ofone or more modified polyamines according to the present invention. Themodified polyamines of the present invention which comprise the fabricenhancement system may be formulated as an admixture wherein aproportional amount of two or more compounds are combined to make up thefabric enhancement system. Alternatively, the formulator may adjust thereaction conditions which form the modified polyamines of the presentinvention in order to create an admixture of suitable ingredients interalia an admixture of polyamine fragments and/or partially crosslinkedmodified polyamines. Whether a formulated admixture or a product byprocess is used, or a mixture of both, the compounds which comprise thefabric enhancement compositions of the present invention have theformula:

i) (PA)_(w)(T)_(x);

ii) (PA)_(w)(L)_(z);

iii) [(PA)_(w)(T)_(x)]_(y)[L]_(z);

wherein PA is a grafted or non-grafted, modified or unmodified polyaminebackbone unit, T is an amide-forming polycarboxylic acid crosslinkingunit, and L is a non-amide forming crosslinking unit. For compounds oftype (i) and (iii) the relative amounts of PA units and T units whichare present are such that the molar ratio of PA units to T units is from0.8:1 to 1.5:1. For compounds of type (ii) the relative amounts of PAunits and L units which are present are such that the (PA)_(w)(L)_(z)comprises from about 0.05, preferably from about 0.3 to 2 parts byweight of said L units. Therefore, 1 part of a grafted or non-grafted,modified or unmodified polyamine backbone unit may be combined with fromabout 0.05, preferably from about 0.3 parts by weight of an L unit toabout 2 parts by weight of an L unit to form a suitable modifiedpolyamine compound. Likewise, for compounds of type (iii), crosslinkedpolyamines having the formula (PA)_(w)(T)_(z) may be combined with fromabout 0.05, preferably from about 0.3 parts by weight of an L unit toabout 2 parts by weight of an L unit to form a suitable modifiedpolyamine compound having the formula [(PA)_(w)(T)_(x)]_(y)[L]_(z).

Polyamine Backbone (PA Units)

The modified polyamine compounds of the present invention comprise aPolyamine Backbone, PA unit, which can be optionally, but preferablygrafted. The following are non-limiting examples of suitable PA unitsaccording to the present invention.

Polyalkyleneimine

A preferred PA unit according to the present invention arepolyalkyleneimines and polyalkyleneamines having the general formula:

wherein R is C₂-C₁₂ linear alkylene, C₃-C₁₂ branched alkylene, andmixtures thereof; B representing a continuation of the chain structureby branching. The indices w, x, and y have various values depending uponsuch factors as molecular weight and relative degree of branching. Thepolyalkyleneimines and polyalkyleneamines which comprise PA units of thepresent invention are divided into three categories based upon relativemolecular weight. The terms polyalkyleneimine and polyalkyleneamine areused interchangeably throughout the present specification and are takento mean polyamines having the general formula indicated above regardlessof method of preparation.

Low Molecular Weight Polyalkyleneimines

For low molecular weight polyalkyleneimines having the formula:

R is C₂-C₁₂ linear alkylene, C₃-C₁₂ branched alkylene, and mixturesthereof; preferably R is ethylene, 1,3-propylene, and 1,6-hexylene, morepreferred is ethylene. The indices w, x, and y are such that themolecular weight of said polyamines does not exceed about 600 daltons.For example, for an entirely linear polyethyleneimine having a molecularweight of about 600 daltons, the index w=1, x=13, and y=0. For anentirely branched polyethyleneimine having a molecular weight ofapproximately 600 daltons, w=8, x=0 and y=7. (This combination ofindices results in a material having an average molecular weight ofabout 646 daltons, which, for the purposes of the present invention is alow molecular weight polyalkyleneimine.) The index w typically has thevalue of y+1. The simplest of the low molecular weight polyamines ofthis type is ethylene diamine which may be present up to about 10% byweight of the PA unit mixture. Non-limiting examples of low molecularweight polyalkyleneimine PA units include diethylene triamine,triethylene tetramine, tetraethylene pentamine, dipropylene triamine,tripropylene tetramine, and dihexamethylene triamine. PA units may beused as crude products or mixtures, and if desired by the formulator,these PA units may be used in the presence of small amounts of diaminesas described herein above, wherein the amount of diamines, inter alia,ethylene diamine, hexamethylene diamine may be present up to about 10%by weight, of the PA unit mixture.

Medium Range Molecular Weight Polyalkyleneimines

For medium range molecular weight polyalkyleneimines having the formula:

R is C₂-C₄ linear alkylene, C₃-C₄ branched alkylene, and mixturesthereof, preferably R is ethylene, 1,3-propylene, and mixtures thereof,more preferred is ethylene wherein said polyamines arepolyethyleneimines (PEI's). The indices w, x, and y are such that themolecular weight of said polyamines is from about 600 daltons to about50,000 daltons. The indices w, x, and y will indicate not only themolecular weight of the polyalkyleneimines but also the degree ofbranching present in the PA unit backbone.

High Molecular Weight Polyalkyleneimines

For high molecular weight polyalkyleneimines having the formula:

R is C₂-C₃ linear alkylene, preferably R is ethylene. The indices w, x,and y are such that the molecular weight of said polyamines is fromabout 50,000 daltons to about 1,000,000 (1 million) daltons. The indicesw, x, and y will indicate not only the molecular weight of thepolyalkyleneimines but also the degree of branching present in the PAunit backbone.

Co-polymeric Polyamines

Another example of a preferred PA unit according to the presentinvention are the polyvinyl amine homo-polymers or co-polymers havingthe formula:

wherein V is a co-monomer, non-limiting examples of which include vinylamides, vinyl pyrrolidone, vinyl imidazole, vinyl esters, vinylalcohols, and mixtures thereof, all of which can be taken together or incombination with polyvinyl amine to form suitable co-polymerizationproducts suitable for use in the fabric enhancement systems of thepresent invention. The indices m and n are such that the copolymerscomprise at least 10%, more preferably at least about 30% of unitsderived from vinyl amine and wherein further the molecular weight ofsaid copolymers if from about 500 daltons, preferably from about 5,000daltons to about 50,000 daltons, preferably to about 20,000 daltons.

Polyamine Backbone Modifications

Optionally but preferably the PA units of the present invention aremodified either before or after reaction with a T unit or L unitcrosslinking agent. The two preferred types of modifications aregrafting and capping.

Preferably the PA units of the present invention are grafted, that isthe PA unit is further reacted with a reagent which elongates said PAunit chain, preferably by reaction of the nitrogens of the PA backboneunit with one or more equivalents of aziridine (ethyleneimine),caprolactam, and mixtures thereof. Grafting units, in contrast to the“capping” units described herein below, can further react on themselvesto provide PA unit chain propagation. An example of a preferred graftedPA unit of the present invention has the formula:

wherein R, B, w, x, and y are the same as defined herein above and G ishydrogen or an extension of the PA unit backbone by grafting.Non-limiting examples of preferred grafting agents are aziridine(ethyleneimine), caprolactam, and mixtures thereof. A preferred graftingagent is aziridine wherein the backbone is extended by units having theformula:

wherein B′ is a continuation by branching wherein the graft does notexceed about 8 units, preferably —CH₂CH₂NH₂ and the value of the indicesp+q have the value from 0, preferably from about 1, more preferably fromabout 2 to about 7, preferably to about 5. Another preferred graftingunit is caprolactam.

The PA units of the present invention can be grafted prior to or aftercrosslinking with one or more T units described herein below, preferablythe grafting is accomplished after crosslinking with said T unit. Thisallows the formulator to take advantage of the differential reactivitybetween the primary and secondary amino units of the PA unit backbonethereby allowing the formulator to controllably link said PA units andto also control the amount of subsequent branching which results fromthe grafting step.

Another optional but preferred PA unit modification is the presence of“capping” units. For example, a PA unit is reacted with an amount of amonocarboxylic acid, non-limiting examples of which are C₁-C₂₂ linear orbranched alkyl, preferably C₁₀-C₁₈ linear alkyl inter alia lauric acid,myristic acid. The amount of capping unit which is reacted with the PAunit is an amount which is sufficient to achieve the desired propertiesof the formula. However, the amount of capping unit used is notsufficient to abate any further crosslinking or grafting which theformulator may choose to perform.

Crosslinking Units

Amide-forming T Crosslinking Units

T crosslinking units are preferably carbonyl comprising polyamidoforming units. The T units are taken together with PA units to formcrosslinked modified polyamine compounds having the formula(PA)_(w)(T)_(x) or [(PA)_(w)(T)_(x)]_(y)[L]_(z).

A preferred embodiment of the present invention includes crosslinked PAunits wherein a T unit provides crosslinking between two or more PAunits to form a (PA)_(w)(T)_(x) polyamido crosslinked section. Apreferred crosslinking T unit has the general formula:

wherein R¹ is methylene, phenylene, and mixtures thereof; preferablymethylene. The index k has the value from 2 to about 8, preferably toabout 4. Preferred values of k are 2, 3, and 4. R² is —NH— therebyforming a urethane amide linkage when said R² comprising T units reactwith the backbone nitrogens of the PA units. The value of the index j isindependently 0 or 1. The presence of R² units can result, for example,from the use of diisocyanates as crosslinking agents. Non-limitingexamples of dibasic acids which are used as a source for T units in theabove formula include succinic acid, maleic acid, adipic acid, glutaricacid, suberic acid, sebacic acid, and terephthalic acid. However, theformulator is not limited to crosslinking T units deriving from dibasicacids, for example, tribasic crosslinking T units, inter alia, citrate,may be used to link the PA units of the present invention.

Examples of (PA)_(w)(T)_(x) compounds according to the present inventionare obtained by condensation of dicarboxylic acids inter alia succinicacid, maleic acid, adipic acid, terephthalic acid, with polyalkylenepolyamines inter alia diethylenetriamine, triethylenetetramine,dipropylenetriamine, tripropylenetetramine wherein the ratio of thedicarboxylic acid to polyalkyleneamine is from 1:0.8 to 1:1.5 moles,preferably a ratio of from 1:0.9 to 1:1.2 moles wherein the resultingcrosslinked material has a viscosity in a 50% by weight, aqueoussolution of more than 100 centipoise at 25° C.

Non-amide Forming L Crosslinking Units

Another preferred embodiment of the polyamines of the present inventionare (PA)_(w)(T)_(x) units which are further crosslinked by L units toform polyamido amines having the formula [(PA)_(w)(T)_(x)]_(y)[L]_(z) orare reacted with PA units to form non-amide polyamines having theformula (PA)_(w)(L)_(z).

The L units of the present invention are any unit which suitablycrosslinks PA units or (PA)_(w)(T)_(x) units. Preferred L linking unitscomprise units which are derived from the use of epihalohydrins,preferably epichlorohydrin, as a crosslinking agent. The epihalohydrinscan be used directly with the PA units or suitably combined with othercrosslinking adjuncts non-limiting examples of which includealkyleneglycols, and polyalkylene polyglycols inter alia ethyleneglycol, diethylene glycol, polyethylene glycol, propylene glycol,dipropylene glycol, polypropylene glycol, butylene glycol,hexanediol-1,6-glycerol, oligoglycerol, pentaerythrites, polyols whichare obtained by the reduction of carbohydrates (sorbitol, mannitol),monosaccharides, disaccharides, oligosaccharides, polysaccharides,polyvinyl alcohols, and mixtures thereof.

For example, a suitable L unit is a dodecylene unit having the formula:

—(CH₂)₁₂—

wherein an equivalent of 1,12-dichlorododecane is reacted, for example,with a suitable amount of a PA unit to produce a polyamine which iscrosslinked via dodecylene units. For the purposes of the presentinvention, L crosslinking units which comprise only carbon and hydrogenare considered to be “hydrocarbyl” L units. Preferred hydrocarbyl unitsare polyalkylene units have the formula:

—(CH₂)_(n)—

wherein n is from 1 to about 50.

Hydrocarbyl L units may be derived from hydrocarbons having two unitswhich are capable of reacting with the nitrogen of the PA units.Non-limiting examples of precursors which result in the formation ofhydrocarbyl L units include 1,6-dibromohexane, 1,8-ditosyloctane, and1,14-dichlorotetradecane.

Further examples of preferred non-amide forming crosslinking L units arethe units which derive from crosslinking units wherein epihalohydrin isused as the connecting unit. For example, 1,12-dihydroxydodecane isreacted with epichlorohydrin to form the bis-epoxide non-amide forming Lunit precursor having the formula:

which when reacted with one or more PA units or (PA)_(w)(T)_(x) unitsresults in an L crosslinking unit having the formula:

however, it is not necessary to pre-form and isolate the bis-epoxide,instead the crosslinking unit precursor may be formed in situ byreaction of 1,12-dihydroxydodecane or other suitable precursor unit withepihalohydrin in the presence of grafted or ungrafted PA units or(PA)_(w)(T)_(x) units.

Other crosslinking L units which utilize one or more epihalohydrinconnecting units include polyalkyleneoxy L units having the formula:

wherein R¹ is ethylene, R² is 1,2-propylene, x is from 0 to 100 and y isfrom 0 to 100.

Another preferred unit which can comprise an L unit and which can besuitably combined with epihalohydrin connecting units includepolyhydroxy units having the formula:

wherein the index t is from at least 2 to about 20 and the index u isfrom 1 to about 6. The formulator may also combine units to form hybridL crosslinking units, for example, units having the formula:

wherein the indexes w and y are each independently from 1 to 50, z isunits are present in a sufficient to suitably connect the polyhydroxyunits and the polyalkyleneoxy units into the backbone without theformation of ether linkages.

The following is an example of an L linking group which comprises both apolyalkyleneoxy and a polyhydroxy unit.

A further example of a preferred crosslinking L units are units whichcomprises at least two aziridine groups as connecting groups, forexample an L unit having the formula:

which can be used to link two (PA)_(w) units, two (PA)_(w)(T)_(x) units,or mixtures thereof.

The polyamines of the present invention may have varying finalcompositions, for example, (PA)_(w)(T)_(x),[(PA)_(w)(T)_(x)]_(y)[L]_(z), [(PA)]_(w)[L]_(z), and mixtures thereof,wherein each PA unit may be grafted or ungrafted. The indices w and xhave values such that the ratio of w to x is from 0.8:1 to 1.5:1; y andz have values such that said polyamido compound comprises from about 0.3to 2 parts by weight of said L unit. In the cases wherein nocrosslinking takes place the indices w and y will be equal to 1 and xand z will be equal to 0. In the case wherein no crosslinking occursusing L units, the index y is equal to 1 and z is equal to 0. In thecase wherein no crosslinking occurs using T units, the indices w and yare equal to 1 and x is equal to 0.

An preferred embodiment of the present invention which comprises PAunits, T units, and L units includes the reaction product of:

a) 1 part by weight, of a polyamine obtained by condensation of 1 moleof a dicarboxylic acid with a polyalkylene polyamine (i.e.,diethylenetriamine) to the extent wherein at least about 10% of the —NHbackbone hydrogens are unmodified by reaction with said dicarboxylicacid, then optionally reacting the obtained polyamine condensationproduct with up to 8 ethyleneimine units (i.e., grafting of the backboneusing aziridine) per basic nitrogen atom; and

b) further reacting the product obtained in (a) with from 0.3 to 2 partsby weight, of an L units, inter alia the reaction product of apolyalkylene oxide having from 8 to 100 alkylene oxide units withepichlorohydrin at a temperature of form about 20° C. to about 100° C.

A preferred embodiment of the present invention are the water-solublecondensation products which can be obtained by the reaction of:

a) polyalkyleneimines and polyalkyleneimines grafted withethyleneimines, and mixtures thereof; with

b) at least bifunctional halogen-free cross-linking agents, said agentsselected from the group consisting of:

i) ethylene carbonate, propylene carbonate, urea, and mixtures thereof;

ii) mono-carboxylic acids comprising one olefin moiety inter aliaacrylic acid, methacrylic acid, crotonic acid; and the esters, amides,and anhydrides thereof; polycarboxylic acids inter alia oxalic acid,succinic acid, tartaric acid, itaconic acid, maleic acid; and theesters, amides, and anhydrides thereof;

iii) reaction products of polyetherdiamines, alkylenediamines,polyalkylenediamines, and mixtures thereof, with mono-carboxylic acidscomprising one olefin moiety wherein the resulting polyamine comprises afunctional units which is selected from the group consisting of at leasttwo ethylenically unsaturated double bonds, carbonamide, carboxyl group,ester group, and mixtures thereof;

iv) at least two aziridine group-containing reaction products ofdicarboxylic acid esters with ethyleneimine and mixtures of thecross-linking agents.

However, prior to reaction of (PA)_(w)(T)_(x) units formed herein above,the (PA)_(w)(T)_(x) polyamine compound may be partially amidated(“capped” as described herein above) by treatment with a mono carboxylicacid or the esters of mono carboxylic acids. The formulator may vary thedegree to which the backbone nitrogens are amidated according to thedesired properties of the final Fabric Enhancement Polymer. Non-limitingexamples of suitable monocarboxylic acids include formic acid, aceticacid, propionic acid, benzoic acid, salicylic acid, lauric acid,palmitic acid, stearic acid, oteic acid, linoleic acid, behenic acid,and mixtures thereof.

The high molecular weight modified polyamine condensation products ofthe present invention (also referred to herein as “resins”) arepreferably formed from the reaction of one or more grafted, cross-linkedpolyethyleneimines and one or more polyethylene and/or polypropyleneglycol copolymers, wherein the resulting crosslinked modified polyamines(resins) have a final viscosity of more than or equal to 300 mPa-sec.,preferably from 400 to 2,500 mPa-sec., when measured at 20° C. in a 20%aqueous solution. The viscosity is determine on 20% strength by weightaqueous solutions at 20° C. in a Haake rotary viscometer, using ashearing rate of 49 sec⁻¹ in the viscosity range below 1000 mPas and of24.5 sec⁻¹ at viscosity above this. Support found in U.S. Pat. No.4,371,674. Col. 4, lines 45-49; Col. 3, lines 59-65. The modifiedpolyamine compounds of the present invention are suitably described inU.S. Pat. No. 3,642,572 Eadres et al., issued Feb. 15, 1972, U.S. Pat.No. 4,144,123 Scharf et al., issued Mar. 13, 1979 and U.S. Pat. No.4,371,674 Hertel et al., issued Feb. 1, 1983, NL 6,612,293, DT1,946,471, DT 36386, DT 733,973, DE 1,771,814, all of which are includedherein by reference.

Laundry Detergent Compositions

The laundry detergent compositions of the present invention take theform which comprises:

a) from about 0.01% by weight, of a fabric enhancement system, saidfabric enhancement system comprising one or more modified polyaminecompounds, said modified polyamine compounds are selected from:

i) PA)_(w)(T)_(x);

ii) (PA)_(w)(L)_(z);

iii) [(PA)_(w)(T)_(λ)]_(y)[L]_(z); and

iv) mixtures thereof;

wherein PA is a grafted or non-grafted, modified or unmodified polyaminebackbone unit, T is an amide-forming polycarboxylic acid crosslinkingunit, and L is a non-amide forming crosslinking unit; provided that forcompounds of type (i) and (iii) the indices w and x have values suchthat the ratio of w to x is from 0.8:1 to 1.5:1; for compounds of type(ii) the indices w and z have values such that said modified polyaminecompound comprises from about 0.05, preferably from about 0.3 to 2 partsby weight of said L unit, for compounds of type (iii) the indices y andz have values such that said modified polyamine compound comprises fromabout 0.05, preferably from about 0.3 to 2 parts by weight of said Lunit;

b) from about 0.01% by weight, of a detersive surfactant selected fromthe group consisting of anionic, cationic, nonionic, zwitterionic,ampholytic surfactants, and mixtures thereof; and

c) the balance carriers and adjunct ingredients, wherein said adjunctingredients are selected from the group consisting of builders, opticalbrighteners, soil release polymers, dye transfer agents, dispersents,enzymes, suds suppressers, dyes, perfumes, colorants, filler salts,hydrotropes, photoactivators, fluorescers, fabric conditioners,hydrolyzable surfactants, preservatives, anti-oxidants, chelants,stabilizers, anti-shrinkage agents, anti-wrinkle agents, germicides,fungicides, anti-corrosion agents, and mixtures thereof.

Surfactant System

The laundry detergent compositions of the present invention may compriseat least about 0.01% by weight, preferably from about 0.1% to about 60%,preferably to about 30% by weight, of a detersive surfactant system,said system is comprised of one or more category of surfactantsdepending upon the embodiment, said categories of surfactants areselected from the group consisting of anionic, cationic, nonionic,zwitterionic, ampholytic surfactants, and mixtures thereof. Within eachcategory of surfactant, more than one type of surfactant of surfactantcan be selected. For example, preferably the solid (i.e. granular) andviscous semi-solid (i.e. gelatinous, pastes, etc.) systems of thepresent invention, surfactant is preferably present to the extent offrom about 0.1% to 60%, preferably to about 30% by weight of thecomposition.

Nonlimiting examples of surfactants useful herein include:

a) C₁₁-C₁₈ alkyl benzene sulfonates (LAS);

b) C₁₀-C₂₀ primary, branched-chain and random alkyl sulfates (AS);

c) C₁₀-C₁₈ secondary (2,3) alkyl sulfates having the formula:

wherein x and (y+1) are integers of at least about 7, preferably atleast about 9; said surfactants disclosed in U.S. Pat. No. 3,234,258Morris, issued Feb. 8, 1966; U.S. Pat. No. 5,075,041 Lutz, issued Dec.24, 1991; U.S. Pat. No. 5,349,101 Lutz et al., issued Sep. 20, 1994; andU.S. Pat. No. 5,389,277 Prieto, issued Feb. 14, 1995 each incorporatedherein by reference;

d) C₁₀-C₁₈ alkyl alkoxy sulfates (AE_(X)S) wherein preferably x is from1-7;

e) C₁₀-C₁₈ alkyl alkoxy carboxylates preferably comprising 1-5 ethoxyunits;

f) C₁₂-C₁₈ alkyl ethoxylates, C₆-C₁₂ alkyl phenol alkoxylates whereinthe alkoxylate units are a mixture of ethyleneoxy and propyleneoxyunits, C₁₂-C₁₈ alcohol and C₆-C₁₂ alkyl phenol condensates with ethyleneoxide/propylene oxide block polymers inter alia Pluronic® ex BASF whichare disclosed in U.S. Pat. No. 3,929,678 Laughlin et al., issued Dec.30, 1975, incorporated herein by reference;

g) Alkylpolysaccharides as disclosed in U.S. Pat. No. 4,565,647 Llenado,issued Jan. 26, 1986, incorporated herein by reference;

h) Polyhydroxy fatty acid amides having the formula:

wherein R⁷ is C₅-C₃₁ alkyl; R⁸ is selected from the group consisting ofhydrogen, C₁-C₄ alkyl, C₁-C₄ hydroxyalkyl, Q is a polyhydroxyalkylmoiety having a linear alkyl chain with at least 3 hydroxyls directlyconnected to the chain, or an alkoxylated derivative thereof; preferredalkoxy is ethoxy or propoxy, and mixtures thereof; preferred Q isderived from a reducing sugar in a reductive amination reaction, morepreferably Q is a glycityl moiety; Q is more preferably selected fromthe group consisting of —CH₂(CHOH)_(n)CH₂OH,—CH(CH₂OH)(CHOH)_(n−1)CH₂OH, —CH₂(CHOH)₂—(CHOR′)(CHOH)CH₂OH, andalkoxylated derivatives thereof, wherein n is an integer from 3 to 5,inclusive, and R′ is hydrogen or a cyclic or aliphatic monosaccharide,which are described in U.S. Pat. No. 5,489,393 Connor et al., issuedFeb. 6, 1996; and U.S. Pat. No. 5,45,982 Murch et al., issued Oct. 3,1995, both incorporated herein by reference.

The laundry detergent compositions of the present invention can alsocomprise from about 0.001% to about 100% of one or more (preferably amixture of two or more) mid-chain branched surfactants, preferablymid-chain branched alkyl alkoxy alcohols having the formula:

mid-chain branched alkyl sulfates having the formula:

and mid-chain branched alkyl alkoxy sulfates having the formula:

wherein the total number of carbon atoms in the branched primary alkylmoiety of these formulae (including the R, R¹, and R² branching, but notincluding the carbon atoms which comprise any EO/PO alkoxy moiety) isfrom 14 to 20, and wherein further for this surfactant mixture theaverage total number of carbon atoms in the branched primary alkylmoieties having the above formula is within the range of greater than14.5 to about 17.5 (preferably from about 15 to about 17); R, R¹, and R²are each independently selected from hydrogen, C₁-C₃ alkyl, and mixturesthereof, preferably methyl; provided R, R¹, and R² are not all hydrogenand, when z is 1, at least R or R¹ is not hydrogen. M is a water solublecation and may comprises more than one type of cation, for example, amixture of sodium and potassium. The index w is an integer from 0 to 13;x is an integer from 0 to 13; y is an integer from 0 to 13; z is aninteger of at least 1; provided w+x+y+z is from 8 to 14. EO and POrepresent ethyleneoxy units and propyleneoxy units having the formula:

respectively, however, other alkoxy units inter alia 1,3-propyleneoxy,butoxy, and mixtures thereof are suitable as alkoxy units appended tothe mid-chain branched alkyl moieties.

The mid-chain branched surfactants are preferably mixtures whichcomprise a surfactant system. Therefore, when the surfactant systemcomprises an alkoxylated surfactant, the index m indicates the averagedegree of alkoxylation within the mixture of surfactants. As such, theindex m is at least about 0.01, preferably within the range of fromabout 0.1, more preferably from 25 about 0.5, most preferably from about1 to about 30, preferably to about 10, more preferably to about 5. Whenconsidering a mid-chain branched surfactant system which comprises onlyalkoxylated surfactants, the value of the index m represents adistribution of the average degree of alkoxylation corresponding to m,or it may be a single specific chain with alkoxylation (e.g.,ethoxylation and/or propoxylation) of exactly the number of unitscorresponding to m.

The preferred mid-chain branched surfactants of the present inventionwhich are suitable for use in the surfactant systems of the presentinvention have the formula:

or the formula:

wherein a, b, d, and e are integers such that a+b is from 10 to 16 andd+e is from 8 to 14; M is selected from sodium, potassium, magnesium,ammonium and substituted ammonium, and mixtures thereof.

The surfactant systems of the present invention which comprise mid-chainbranched surfactants are preferably formulated in two embodiments. Afirst preferred embodiment comprises mid-chain branched surfactantswhich are formed from a feedstock which comprises 25% or less ofmid-chain branched alkyl units. Therefore, prior to admixture with anyother conventional surfactants, the mid-chain branched surfactantcomponent will comprise 25% or less of surfactant molecules which arenon-linear surfactants.

A second preferred embodiment comprises mid-chain branched surfactantswhich are formed from a feedstock which comprises from about 25% toabout 70% of mid-chain branched alkyl units. Therefore, prior toadmixture with any other conventional surfactants, the mid-chainbranched surfactant component will comprise from about 25% to about 70%surfactant molecules which are non-linear surfactants.

The surfactant systems of the laundry detergent compositions of thepresent invention can also comprise from about 0.001%, preferably fromabout 1%, more preferably from about 5%, most preferably from about 10%to about 100%, preferably to about 60%, more preferably to about 30% byweight, of the surfactant system, of one or more (preferably a mixtureof two or more) mid-chain branched alkyl arylsulfonate surfactants,preferably surfactants wherein the aryl unit is a benzene ring havingthe formula:

wherein L is an acyclic hydrocarbyl moiety comprising from 6 to 18carbon atoms; R¹, R², and R³ are each independently hydrogen or C₁-C₃alkyl, provided R¹ and R² are not attached at the terminus of the Lunit; M is a water soluble cation having charge q wherein a and b aretaken together to satisfy charge neutrality.

Adjunct Ingredients

The following are non-limiting examples of adjunct ingredients useful inthe laundry compositions of the present invention, said adjunctingredients include builders, optical brighteners, soil releasepolymers, dye transfer agents, dispersents, enzymes, suds suppressers,dyes, perfumes, colorants, filler salts, hydrotropes, photoactivators,fluorescers, fabric conditioners, hydrolyzable surfactants,preservatives, anti-oxidants, chelants, stabilizers, anti-shrinkageagents, anti-wrinkle agents, germicides, fungicides, anti corrosionagents, and mixtures thereof.

Builders—The laundry detergent compositions of the present inventionpreferably comprise one or more detergent builders or builder systems.When present, the compositions will typically comprise at least about 1%builder, preferably from about 5%, more preferably from about 10% toabout 80%, preferably to about 50%, more preferably to about 30% byweight, of detergent builder.

The level of builder can vary widely depending upon the end use of thecomposition and its desired physical form. When present, thecompositions will typically comprise at least about 1% builder.Formulations typically comprise from about 5% to about 50%, moretypically about 5% to about 30%, by weight, of detergent builder.Granular formulations typically comprise from about 10% to about 80%,more typically from about 15% to about 50% by weight, of the detergentbuilder. Lower or higher levels of builder, however, are not meant to beexcluded.

Inorganic or P-containing detergent builders include, but are notlimited to, the alkali metal, ammonium and alkanolammonium salts ofpolyphosphates (exemplified by the tripolyphosphates, pyrophosphates,and glassy polymeric meta-phosphates), phosphonates, phytic acid,silicates, carbonates (including bicarbonates and sesquicarbonates),sulphates, and aluminosilicates. However, non-phosphate builders arerequired in some locales. Importantly, the compositions herein functionsurprisingly well even in the presence of the so-called “weak” builders(as compared with phosphates) such as citrate, or in the so-called“underbuilt” situation that may occur with zeolite or layered silicatebuilders.

Examples of silicate builders are the alkali metal silicates,particularly those having a SiO₂:Na₂O ratio in the range 1.6:1 to 3.2:1and layered silicates, such as the layered sodium silicates described inU.S. Pat. No. 4,664,839 Rieck, issued May 12, 1987. NaSKS-6 is thetrademark for a crystalline layered silicate marketed by Hoechst(commonly abbreviated herein as “SKS-6”). Unlike zeolite builders, theNa SKS-6 silicate builder does not contain aluminum. NaSKS-6 has thedelta-Na₂SiO₅ morphology form of layered silicate. It can be prepared bymethods such as those described in German DE-A-3,417,649 andDE-A-3,742,043. SKS-6 is a highly preferred layered silicate for useherein, but other such layered silicates, such as those having thegeneral formula NaMSi_(x)O_(2x+1)._(y)H₂O wherein M is sodium orhydrogen, x is a number from 1.9 to 4, preferably 2, and y is a numberfrom 0 to 20, preferably 0 can be used herein. Various other layeredsilicates from Hoechst include NaSKS-5, NaSKS-7 and NaSKS-11, as thealpha, beta and gamma forms. As noted above, the delta-Na₂SiO₅ (NaSKS-6form) is most preferred for use herein. Other silicates may also beuseful such as for example magnesium silicate, which can serve as acrispening agent in granular formulations, as a stabilizing agent foroxygen bleaches, and as a component of suds control systems.

Examples of carbonate builders are the alkaline earth and alkali metalcarbonates as disclosed in German Patent Application No. 2,321,001published on Nov. 15, 1973.

Aluminosilicate builders are useful in the present invention.Aluminosilicate builders are of great importance in most currentlymarketed heavy duty granular detergent compositions, and can also be asignificant builder ingredient in liquid detergent formulations.Aluminosilicate builders include those having the empirical formula:

[M_(z)(zAlO₂)_(y)].xH₂O

wherein z and y are integers of at least 6, the molar ratio of z to y isin the range from 1.0 to about 0.5, and x is an integer from about 15 toabout 264.

Useful aluminosilicate ion exchange materials are commerciallyavailable. These aluminosilicates can be crystalline or amorphous instructure and can be naturally-occurring aluminosilicates orsynthetically derived. A method for producing aluminosilicate ionexchange materials is disclosed in U.S. Pat. No. 3,985,669, Krummel etal, issued Oct. 12, 1976. Preferred synthetic crystallinealuminosilicate ion exchange materials useful herein are available underthe designations Zeolite A, Zeolite P (B), Zeolite MAP and Zeolite X. Inan especially preferred embodiment, the crystalline aluminosilicate ionexchange material has the formula:

Na₁₂[(AlO₂)₁₂(SiO₂)₁₂].xH₂O

wherein x is from about 20 to about 30, especially about 27. Thismaterial is known as Zeolite A. Dehydrated zeolites (x=0-10) may also beused herein. Preferably, the aluminosilicate has a particle size ofabout 0.1-10 microns in diameter.

Organic detergent builders suitable for the purposes of the presentinvention include, but are not restricted to, a wide variety ofpolycarboxylate compounds. As used herein, “poly-carboxylate” refers tocompounds having a plurality of carboxylate groups, preferably at least3 carboxylates. Polycarboxylate builder can generally be added to thecomposition in acid form, but can also be added in the form of aneutralized salt. When utilized in salt form, alkali metals, such assodium, potassium, and lithium, or alkanolammonium salts are preferred.

Included among the polycarboxylate builders are a variety of categoriesof useful materials. One important category of polycarboxylate buildersencompasses the ether polycarboxylates, including oxydisuccinate, asdisclosed in U.S. Pat. No. 3,128,287 Berg, issued Apr. 7, 1964, and U.S.Pat. No. 3,635,830 Lamberti et al., issued Jan. 18, 1972. See also“TMS/TDS” builders of U.S. Pat. No. 4,663,071 Bush et al., issued May 5,1987. Suitable ether polycarboxylates also include cyclic compounds,particularly alicyclic compounds, such as those described in U.S. Pat.No. 3,923,679 Rapko, issued Dec. 2, 1975; U.S. Pat. No. 4,158,635Crutchfield et al., issued Jun. 19, 1979; U.S. Pat. No. 4,120,874Crutchfield et al., issued Oct. 17, 1978; and U.S. Pat. No. 4,102,903Crutchfield et al., issued Jul. 25, 1978.

Other useful detergency builders include the etherhydroxypolycarboxylates, copolymers of maleic anhydride with ethylene orvinyl methyl ether, 1,3,5-trihydroxy benzene-2,4,6-trisulphonic acid,and carboxymethyloxysuccinic acid, the various alkali metal, ammoniumand substituted ammonium salts of polyacetic acids such asethylenediamine tetraacetic acid and nitrilotriacetic acid, as well aspolycarboxylates such as mellitic acid, succinic acid, oxy-disuccinicacid, polymaleic acid, benzene 1,3,5-tricarboxylic acid,carboxymethyloxysuccinic acid, and soluble salts thereof.

Citrate builders, e.g., citric acid and soluble salts thereof(particularly sodium salt), are polycarboxylate builders of particularimportance for heavy duty liquid detergent formulations due to theiravailability from renewable resources and their biodegradability.Citrates can also be used in granular compositions, especially incombination with zeolite and/or layered silicate builders.Oxydisuccinates are also especially useful in such compositions andcombinations.

Also suitable in the detergent compositions of the present invention arethe 3,3-dicarboxy-4-oxa-1,6-hexanedioates and the related compoundsdisclosed in U.S. Pat. No. 4,566,984, Bush, issued Jan. 28, 1986. Usefulsuccinic acid builders include the C₅-C₂₀ alkyl and alkenyl succinicacids and salts thereof. A particularly preferred compound of this typeis do-decenylsuccinic acid. Specific examples of succinate buildersinclude: laurylsuccinate, myristylsuccinate, palmitylsuccinate,2-dodecenylsuccinate (preferred), 2-pentadecenylsuccinate, and the like.Laurylsuccinates are the preferred builders of this group, and aredescribed in European Patent Application 86200690.5/0,200,263, publishedNov. 5, 1986.

Other suitable polycarboxylates are disclosed in U.S. Pat. No.4,144,226, Crutchfield et al., issued Mar. 13, 1979 and in U.S. Pat. No.3,308,067, Diehl, issued Mar. 7, 1967. See also Diehl U.S. Patent No.3,723,322.

Fatty acids, e.g., C₁₂-C₁₈ monocarboxylic acids, can also beincorporated into the compositions alone, or in combination with theaforesaid builders, especially citrate and/or the succinate builders, toprovide additional builder activity. Such use of fatty acids willgenerally result in a diminution of sudsing, which should be taken intoaccount by the formulator.

In situations where phosphorus-based builders can be used, andespecially in the formulation of bars used for hand-launderingoperations, the various alkali metal phosphates such as the well-knownsodium tripolyphosphates, sodium pyrophosphate and sodium orthophosphatecan be used. Phosphonate builders such asethane-1-hydroxy-1,1-diphosphonate and other known phosphonates (see,for example, U.S. Pat. No. 3,159,581; 3,213,030; 3,422,021; 3,400,148and 3,422,137) can also be used.

Dispersants

A description of other suitable polyalkyleneimine dispersants which maybe optionally combined with the bleach stable dispersants of the presentinvention can be found in U.S. Pat. No. 4,597,898 Vander Meer, issuedJul. 1, 1986; European Patent Application 111,965 Oh and Gosselink,published Jun. 27, 1984; European Patent Application 111,984 Gosselink,published Jun. 27, 1984; European Patent Application 112,592 Gosselink,published Jul. 4, 1984; U.S. Pat. No. 4,548,744 Connor, issued Oct. 22,1985; and U.S. Pat. No. 5,565,145 Watson et al., issued Oct. 15, 1996;all of which are included herein by reference. However, any suitableclay/soil dispersant or anti-redepostion agent can be used in thelaundry compositions of the present invention.

In addition, polymeric dispersing agents which include polymericpolycarboxylates and polyethylene glycols, are suitable for use in thepresent invention. Polymeric polycarboxylate materials can be preparedby polymerizing or copolymerizing suitable unsaturated monomers,preferably in their acid form. Unsaturated monomeric acids that can bepolymerized to form suitable polymeric polycarboxylates include acrylicacid, maleic acid (or maleic anhydride), fumaric acid, itaconic acid,aconitic acid, mesaconic acid, citraconic acid and methylenemalonicacid. The presence in the polymeric polycarboxylates herein or monomericsegments, containing no carboxylate radicals such as vinylmethyl ether,styrene, ethylene, etc. is suitable provided that such segments do notconstitute more than about 40% by weight.

Particularly suitable polymeric polycarboxylates can be derived fromacrylic acid. Such acrylic acid-based polymers which are useful hereinare the water-soluble salts of polymerized acrylic acid. The averagemolecular weight of such polymers in the acid form preferably rangesfrom about 2,000 to 10,000, more preferably from about 4,000 to 7,000and most preferably from about 4,000 to 5,000. Water-soluble salts ofsuch acrylic acid polymers can include, for example, the alkali metal,ammonium and substituted ammonium salts. Soluble polymers of this typeare known materials. Use of polyacrylates of this type in detergentcompositions has been disclosed, for example, in Diehl, U.S. Pat. No.3,308,067, issued Mar. 7, 1967.

Acrylic/maleic-based copolymers may also be used as a preferredcomponent of the dispersing/anti-redeposition agent. Such materialsinclude the water-soluble salts of copolymers of acrylic acid and maleicacid. The average molecular weight of such copolymers in the acid formpreferably ranges from about 2,000, preferably from about 5,000, morepreferably from about 7,000 to 100,000, more preferably to 75,000, mostpreferably to 65,000. The ratio of acrylate to maleate segments in suchcopolymers will generally range from about 30:1 to about 1:1, morepreferably from about 10:1 to 2:1. Water-soluble salts of such acrylicacid/maleic acid copolymers can include, for example, the alkali metal,ammonium and substituted ammonium salts. Soluble acrylate/maleatecopolymers of this type are known materials which are described inEuropean Patent Application No. 66915, published Dec. 15, 1982, as wellas in EP 193,360, published Sep. 3, 1986, which also describes suchpolymers comprising hydroxypropylacrylate. Still other useful dispersingagents include the maleic/acrylic/vinyl alcohol terpolymers. Suchmaterials are also disclosed in EP 193,360, including, for example, the45/45/10 terpolymer of acrylic/maleic/vinyl alcohol.

Another polymeric material which can be included is polyethylene glycol(PEG). PEG can exhibit dispersing agent performance as well as act as aclay soil removal-antiredeposition agent. Typical molecular weightranges for these purposes range from about 500 to about 100,000,preferably from about 1,000 to about 50,000, more preferably from about1,500 to about 10,000.

Polyaspartate and polyglutamate dispersing agents may also be used,especially in conjunction with zeolite builders. Dispersing agents suchas polyaspartate preferably have a molecular weight (avg.) of about10,000.

Soil Release Agents

The compositions according to the present invention may optionallycomprise one or more soil release agents. If utilized, soil releaseagents will generally comprise from about 0.01%, preferably from about0.1%, more preferably from about 0.2% to about 10%, preferably to about5%, more preferably to about 3% by weight, of the composition. Polymericsoil release agents are characterized by having both hydrophilicsegments, to hydrophilize the surface of hydrophobic fibers, such aspolyester and nylon, and hydrophobic segments, to deposit uponhydrophobic fibers and remain adhered thereto through completion of thelaundry cycle and, thus, serve as an anchor for the hydrophilicsegments. This can enable stains occuring subsequent to treatment withthe soil release agent to be more easily cleaned in later washingprocedures.

The following, all included herein by reference, describe soil releasepolymers suitable for use in the present invention. U.S. Pat. No.5,728,671 Rohrbaugh et al., issued Mar. 17, 1998; U.S. Pat. No.5,691,298 Gosselink et al., issued Nov. 25, 1997; U.S. Pat. No.5,599,782 Pan et al., issued Feb. 4, 1997; U.S. Pat. No. 5,415,807Gosselink et al., issued May 16, 1995; U.S. Pat. No. 5,182,043 Morrallet al., issued Jan. 26, 1993; U.S. Pat. No. 4,956,447 Gosselink et al.,issued Sep. 11, 1990; U.S. Pat. No. 4,976,879 Maldonado et al., issuedDec. 11, 1990; U.S. Pat. No. 4,968,451 Scheibel et al., issued Nov. 6,1990; U.S. Pat. No. 4,925,577 Borcher, Sr. et al., issued May 15, 1990;U.S. Pat. No. 4,861,512 Gosselink, issued Aug. 29, 1989; U.S. Pat. No.4,877,896 Maldonado et al., issued Oct. 31, 1989; U.S. Pat. No.4,771,730 Gosselink et al., issued Oct. 27, 1987; U.S. Pat. No. 711,730Gosselink et al., issued Dec. 8, 1987; U.S. Pat. No. 4,721,580 Gosselinkissued Jan. 26, 1988; U.S. Pat. No. 4,000,093 Nicol et al., issued Dec.28, 1976; U.S. Pat. No. 3,959,230 Hayes, issued May 25, 1976; U.S. Pat.No. 3,893,929 Basadur, issued Jul. 8, 1975; and European PatentApplication 0 219 048, published Apr. 22, 1987 by Kud et al.

Further suitable soil release agents are described in U.S. Pat. No.4,201,824 Voilland et al.; U.S. Pat. No. 4,240,918 Lagasse et al.; U.S.Pat. No. 4,525,524 Tung et al.; U.S. Pat. No. 4,579,681 Ruppert et al.;U.S. Pat. No. 4,220,918; U.S. Pat. No. 4,787,989; EP 279,134 A, 1988 toRhone-Poulenc Chemie; EP 457,205 A to BASF (1991); and DE 2,335,044 toUnilever N.V., 1974; all incorporated herein by reference.

As a non-limiting example, granular compositions are generally made bycombining base granule ingredients, e.g., surfactants, builders, water,etc., as a slurry, and spray drying the resulting slurry to a low levelof residual moisture (5-12%). The remaining dry ingredients, e.g.,granules of the polyalkyleneimine dispersant, can be admixed in granularpowder form with the spray dried granules in a rotary mixing drum. Theliquid ingredients, e.g., solutions of the polyalkyleneimine dispersant,enzymes, binders and perfumes, can be sprayed onto the resultinggranules to form the finished detergent composition. Granularcompositions according to the present invention can also be in “compactform”, i.e. they may have a relatively higher density than conventionalgranular detergents, i.e. from 550 to 950 g/l. In such case, thegranular detergent compositions according to the present invention willcontain a lower amount of “inorganic filler salt”, compared toconventional granular detergents; typical filler salts are alkalineearth metal salts of sulphates and chlorides, typically sodium sulphate;“compact” detergents typically comprise not more than 10% filler salt.

Liquid detergent compositions can be prepared by admixing the essentialand optional ingredients thereof in any desired order to providecompositions containing components in the requisite concentrations.Liquid compositions according to the present invention can also be in“compact form”, in such case, the liquid detergent compositionsaccording to the present invention will contain a lower amount of water,compared to conventional liquid detergents. Addition of thepolyalkyleneimine dispersant to liquid detergent or other aqueouscompositions of this invention may be accomplished by simply mixing intothe liquid solutions the polyalkyleneimine dispersant.

The compositions of the present invention can be suitably prepared byany process chosen by the formulator, non-limiting examples of which aredescribed in U.S. Pat. No. 5,691,297 Nassano et al., issued Nov. 11,1997; U.S. Pat. No. 5,574,005 Welch et al., issued Nov. 12, 1996; U.S.Pat. No. 5,569,645 Dinniwell et al., issued Oct. 29, 1996; U.S. Pat. No.5,565,422 Del Greco et al., issued Oct. 15, 1996; U.S. Pat. No.5,516,448 Capeci et al., issued May 14, 1996; U.S. Pat. No. 5,489,392Capeci et al., issued Feb. 6, 1996; U.S. Pat. No. 5,486,303 Capeci etal., issued Jan. 23, 1996 all of which are incorporated herein byreference.

Method of Use

The present invention also relates to a method for using the laundrydetergent or pre-soak compositions to suitably clean fabric.

The methods of the present invention include a method for cleaningfabric comprising the step of contacting fabric in need of cleaning withan aqueous solution containing a least 50 ppm, preferably at least about100 ppm, more preferably at least about 200 ppm, of a laundry detergentcomposition which comprises:

a) from about 0.01% by weight, of a detersive surfactant selected fromthe group consisting of anionic, cationic, nonionic, zwitterionic,ampholytic surfactants, and mixtures thereof;

b) from about 0.01% by weight, of a fabric enhancement system, saidfabric enhancement system comprising one or more modified polyaminecompounds, said modified polyamine compounds are selected from:

i) (PA)_(w)(T)_(x);

ii) (PA)_(w)(L)_(z);

iii) [(PA)_(w)(T)_(x)]_(y)[L]_(z); and

iv) mixtures thereof;

wherein PA is a grafted or non-grafted, modified or unmodified polyaminebackbone unit, T is an amide-forming polycarboxylic acid crosslinkingunit, and L is a non-amide forming crosslinking unit; provided that forcompounds of type (i) and (iii) the indices w and x have values suchthat the ratio of w to x is from 0.8:1 to 1.5:1; for compounds of type(ii) the indices w and z have values such that said modified polyaminecompound comprises from about 0.05, preferably from about 0.3 to 2 partsby weight of said L unit; for compounds of type (iii) the indices y andz have values such that said modified polyamine compound comprises fromabout 0.05, preferably from about 0.3 to 2 parts by weight of said Lunit; and

c) the balance carriers and adjunct ingredients.

The detergent compositions according to the present invention can be inliquid, paste, laundry bar, or granular form. Such compositions can beprepared by combining the essential and optional components in therequisite concentrations in any suitable order and by any conventionalmeans.

The following is an example of laundry detergent compositions whichcomprise a fabric enhancement system of the present invention.

TABLE I weight % Ingredients 1 2 3 4 Polyhydroxy coco-fatty acid amide2.50 4.00 4.50 — NEODOL 24-7¹ — 4.50 — — NEODOL 23-9² 0.63 — 4.50 2.00C₂₅ Alkyl ethoxylate sulphate 20.15 4.00 5.50 20.50 C₂₅ Alkyl sulfate —14.00 15.00 — C11.8 linear alkylbenzene — — — 6.00 sulfonateC₈₋₁₀-Amidopropyl Amine — 1.30 — — C₁₀-Amidopropyl Amine 0.50 — — 1.50Citric acid 3.00 2.00 3.00 2.50 C12-18 fatty acid 2.00 6.50 5.00 5.00Rapeseed fatty acid — 4.10 — 6.50 Ethanol 3.36 1.53 5.60 0.50Propanediol 7.40 9.20 6.22 4.00 Monoethanolamine 1.00 7.90 8.68 0.50Sodium hydroxide 2.75 1.30 0.75 4.40 Sodium p-toluene sulfonate 2.25 —1.90 — Borax/Boric acid 2.50 2.00 3.50 2.50 Protease³ 0.88 0.74 1.500.88 Lipolase⁴ — 0.12 0.18 — Duramyl⁵ 0.15 0.11 — 0.15 CAREZYME 0.0530.028 0.080 0.053 Dispersant⁶ 0.60 0.70 1.50 0.60 Ethoxylatedpolyalkyleneimine⁷ 1.20 0.70 1.50 1.20 Optical Brightener 0.13 0.15 0.300.15 Polyamine⁸ 5.00 1.00 — — Polyamine⁹ — — 0.25 0.50 Suds suppresser0.12 0.28 0.12 0.12 Minors, aesthetics, stabilizers, balance balancebalance balance water ¹C₁₂-C₁₄ alkyl ethoxylate as sold by Shell Oil Co.²C₁₂-C₁₃ alkyl ethoxylate as sold by Shell Oil Co. ³Protease B variantof BPN′ wherein Tyr 17 is replaced with Leu. ⁴Derived from Humicolalanuginosa and commercially available from Novo. ⁵Disclosed in WO9510603 A and available from Novo. ⁶Hydrophilic dispersant PEI 189E₁₅-E₁₈ according to U.S. Pat. No. 4,597,898, Vander Meer, issued July1, 1986. ⁷Polyalkyleneimine dispersant PEI 600 E₂₀. ⁸Lupasol ® SK exBASF. ⁹Lupasol ® SKA ex BASF.

What is claimed is:
 1. A laundry detergent composition comprising: a)from about 0.01% to about 20% by weight, of a fabric enhancement system,said fabric enhancement system comprising one or more modified polyaminecompounds having a molecular weight of from about 2,500,000 Daltons toabout 10,000,000 Daltons, said modified polyamine compounds are selectedfrom: i) (PA)_(w)(T)_(x); ii) (PA)_(w)(L)_(z); iii)[(PA)_(w)(T)_(x)]_(y)[L]_(z); and iv) mixtures thereof; wherein PA is agrafted or non-grafted, modified or unmodified polyamine backbone unit,T is an amide-forming polycarboxylic acid crosslinking unit, and L is anon-amide forming crosslinking unit; provided that for compounds of type(i) and (iii) the indices w and x have values such that the ratio of wto x is from 0.8:1 to 1.5:1; for compounds of type (ii) the indices wand z have values such that said modified polyamine compound comprisesfrom about 0.05 to 2 parts by weight of said L unit; for compounds oftype (iii) the indices y and z have values such that said modifiedpolyamine compound comprises from about 0.05 to 2 parts by weight ofsaid L unit; b) from about 0.01% to about 60% by weight, of a detersivesurfactant selected from the group consisting of anionic, cationic,nonionic, zwitterionic, ampholytic surfactants, and mixtures thereof;and c) the balance carriers and adjunct ingredients.
 2. A compositionaccording to claim 1 wherein said PA polyamine backbone unit comprises apolyamine which is grafted wherein said grafting agent is selected fromaziridine, caprolactam, and mixtures thereof.
 3. A composition accordingto claim 1 wherein said T unit has the formula:

wherein R¹ is methylene, phenylene, and mixtures thereof; R² is —NH—; kis from 2 to 8, each j is independently 0 or
 1. 4. A compositionaccording to claim 1 wherein said L unit is selected from: i)polyalkylene units having the formula: —(CH₂)_(n)— wherein n is from 1to about 50; ii) epihalohydrin/polyalkylene units having the formula:

 wherein n is from 1 to 50; iii) polyalkyleneoxy comprising units havingthe formula:

 wherein R¹ is ethylene, R² is 1,2-propylene, x is from 0 to 100 and yis from 0 to 100; iv) polyhydroxy comprising units having the formula:

 wherein the index t is at least 2 and the index u is from 1 to about 6;v) polyalkyleneoxy/polyhydroxy comprising units having the formula;

 wherein R¹, R², t, u, x, and y are the same as defined above, theindexes w and z are each independently from 1 to 50; vi) units whichcomprise an aziridine unit having the formula:

 wherein h is from 0 to 22; and vii) mixtures thereof.
 5. A compositionaccording to claim 1 wherein said polyamine compound is formed by thereaction of: a) 1 part by weight, of a polyamidoamine obtained bycondensation of 1 mole of a dicarboxylic acid with from 0.8 to 1.5 molesof a polyalkylene polyamine then optionally reacting the obtainedpolyamidoamine condensation product with up to 8 ethyleneimine units perbasic nitrogen atom; and b) further reacting the product obtained in (a)with from 0.05 to 2 parts by weight, of a reaction product of apolyalkylene oxide having from 8 to 100 alkylene oxide units withepichlorohydrin at a temperature of form about 20° C. to about 100° C.6. A composition according to claim 1 wherein said adjunct ingredientsare selected from the group consisting of builders, optical brighteners,soil release polymers, dye transfer agents, dispersents, enzymes, sudssuppressers, dyes, perfumes, colorants, filler salts, hydrotropes,photoactivators, fluorescers, fabric conditioners, hydrolyzablesurfactants, preservatives, anti-oxidants, chelants, stabilizers,anti-shrinkage agents, anti-wrinkle agents, germicides, fungicides, anticorrosion agents, and mixtures thereof.
 7. A composition according toclaim 1 further comprising at least 1% by weight, of a builder.
 8. Alaundry detergent composition comprising: a) from about 0.01% to about20% by weight, of a fabric enhancement system, said fabric enhancementsystem comprising one or more modified polyamine compounds having amolecular weight of from about 2,500,000 Daltons to about 10,000,000Daltons, said modified polyamine compounds are selected from: i)(PA)_(w)(T)_(x); ii) (PA)_(w)(L)_(z); iii) [(PA)_(w)(T)_(x)]_(y)[L]_(z);and iv) mixtures thereof; wherein PA is a grafted or non-grafted,modified or unmodified polyamine backbone unit, T is an amide-formingpolycarboxylic acid crosslinking unit, and L is a non-amide formingcrosslinking unit; provided that for compounds of type (i) and (iii) theindices w and x have values such that the ratio of w to x is from 0.8:1to 1.5:1; for compounds of type (ii) the indices w and z have valuessuch that said modified polyamine compound comprises from about 0.05 to2 parts by weight of said L unit; for compounds of type (iii) theindices y and z have values such that said modified polyamine compoundcomprises from about 0.05 to 2 parts by weight of said L unit; b) fromabout 0.01% to about 60% by weight, of a detersive surfactant selectedfrom the group consisting of anionic, cationic, nonionic, zwitterionic,ampholytic surfactants, and mixtures thereof; c) from about 1% to about30% by weight, of a bleaching system; and d) the balance carriers andadjunct ingredients.
 9. A composition according to claim 8 wherein saidadjunct ingredients are selected from the group consisting of builders,optical brighteners, soil release polymers, dye transfer agents,dispersents, enzymes, suds suppressers, dyes, perfumes, colorants,filler salts, hydrotropes, photoactivators, fluorescers, fabricconditioners, hydrolyzable surfactants, preservatives, anti-oxidants,chelants, stabilizers, anti-shrinkage agents, anti-wrinkle agents,germicides, fungicides, anti corrosion agents, and mixtures thereof. 10.A composition according to claim 8 wherein said bleaching systemcomprises: i) a source of hydrogen peroxide, said source of hydrogenperoxide is selected from the group consisting of hydrogen peroxide,sodium perborate, sodium carbonate peroxyhydrate, sodium pyrophosphateperoxyhydrate, urea peroxyhydrate, sodium peroxide, and mixturesthereof; and ii) a bleach activater selected from the group consistingof tetraacetyl ethylene diamine, benzoylcaprolactam,4-nitrobenzoylcaprolactam, 3-chlorobenzoylcaprolactam,benzoyloxybenzenesulphonate, nonanoyloxybenzenesulphonate, phenylbenzoate, decanoyloxybenzenesulphonate, dodecanoyloxybenzenesulphonate,benzoylvalerolactam, octanoyloxybenzenesulphonate, decanoyloxybenzoicacid, perhydrolyzable esters and mixtures thereof.
 11. A compositionaccording to claim 8 further comprising at least 1% by weight, of abuilder.
 12. A composition according to claim 8 further comprising atleast 0.01% by weight of a soil release agent.
 13. A laundry detergentcomposition comprising: a) from about 0.01% to about 20% by weight, of afabric enhancement system, said fabric enhancement system comprising oneor more modified polyamine compounds having a molecular weight of fromabout 2,500,000 Daltons to about 10,000,000 Daltons, said modifiedpolyamine compounds are selected from: i) (PA)_(w)(T)_(x); ii)(PA)_(w)(L)_(z); iii) [(PA)_(w)(T)_(x)]_(y)[L]_(z); and iv) mixturesthereof; wherein PA is a grafted or non-grafted, modified or unmodifiedpolyamine backbone unit, T is an amide-forming polycarboxylic acidcrosslinking unit, and L is a non-amide forming crosslinking unit;provided that for compounds of type (i) and (iii) the indices w and xhave values such that the ratio of w to x is from 0.8:1 to 1.5:1; forcompounds of type (ii) the indices w and z have values such that saidmodified polyamine compound comprises from about 0.05 to 2 parts byweight of said L unit; for compounds of type (iii) the indices y and zhave values such that said modified polyamine compound comprises fromabout 0.05 to 2 parts by weight of said L unit; b) from about 0.01% toabout 60% by weight, of a detersive surfactant selected from the groupconsisting of anionic, cationic, nonionic, zwitterionic, ampholyticsurfactants, and mixtures thereof; c) from about 1% to about 30% byweight of a bleaching system, said bleaching system comprising: i) asource of hydrogen peroxide; ii) a bleach activator; and d) the balancecarriers and adjunct ingredients, said adjunct ingredients are selectedfrom the group consisting of builders, optical brighteners, soil releasepolymers, dye transfer agents, dispersents, enzymes, suds suppressers,dyes, perfumes, colorants, filler salts, hydrotropes, photoactivators,fluorescers, fabric conditioners, hydrolyzable surfactants,preservatives, anti-oxidants, chelants, stabilizers, anti-shrinkageagents, anti-wrinkle agents, germicides, fungicides, anti corrosionagents, and mixtures thereof.
 14. A composition according to claim 13wherein said source of hydrogen peroxide is selected from the groupconsisting of sodium perborate, sodium carbonate, and mixtures thereofand said bleach activator is selected from the group consisting oftetraacetyl ethylene diamine, benzoylcaprolactam,nonanoyloxybenzenesulphonate, benzoylvalerolactam, and mixtures thereof.15. A method for cleaning fabric comprising the step of contactingfabric in need of cleaning with an aqueous solution containing a least50 ppm of a laundry detergent composition which comprises: a) from about0.01% to about 20% by weight, of a fabric enhancement system, saidfabric enhancement system comprising one or more modified polyaminecompounds having a molecular weight of from about 2,500,000 Daltons toabout 10,000,000 Daltons, said modified polyamine compounds are selectedfrom: i) (PA)_(w)(T)_(x); ii) (PA)_(w)(L)_(z); iii)[(PA)_(w)(T)_(x)]_(y)[L]_(z); and iv) mixtures thereof; wherein PA is agrafted or non-grafted, modified or unmodified polyamine backbone unit,T is an amide-forming polycarboxylic acid crosslinking unit, and L is anon-amide forming crosslinking unit; provided that for compounds of type(i) and (iii) the indices w and x have values such that the ratio of wto x is from 0.8:1 to 1.5:1; for compounds of type (ii) the indices wand z have values such that said modified polyamine compound comprisesfrom about 0.05 to 2 parts by weight of said L unit; for compounds oftype (iii) the indices y and z have values such that said modifiedpolyamine compound comprises from about 0.05 to 2 parts by weight ofsaid L unit; b) from about 0.01% to about 60% by weight, of a detersivesurfactant selected from the group consisting of anionic, cationic,nonionic, zwitterionic, ampholytic surfactants, and mixtures thereof;and c) the balance carriers and adjunct ingredients.
 16. A methodaccording to claim 15 wherein said PA polyamine backbone unit comprisesa polyamine which is grafted wherein said grafting agent is selectedfrom aziridine, caprolactam, and mixtures thereof.
 17. A methodaccording to claim 15 wherein said T unit has the formula:

wherein R¹ is methylene, phenylene, and mixtures thereof; R² is —NH—; kis from 2 to 8, each j is independently 0 or
 1. 18. A compositionaccording to claim 14 wherein said L unit is selected from: i)polyalkylene units having the formula: —(CH₂)_(n)—  wherein n is from 1to about 50; ii) epihalohydrin/polyalkylene units having the formula:

 wherein n is from 1 to 50; iii) polyalkyleneoxy comprising units havingthe formula:

 wherein R¹ is ethylene, R² is 1,2-propylene, x is from 0 to 100 and yis from 0 to 100; iv) polyhydroxy comprising units having the formula:

 wherein the index t is at least 2 and the index u is from 1 to about 6;v) polyalkyleneoxy/polyhydroxy comprising units having the formula;

 wherein R¹, R², t, u, x, and y are the same as defined above, theindexes w and z are each independently from 1 to 50; vi) units whichcomprise an aziridine unit having the formula:

 wherein h is from 0 to 22; and vii) mixtures thereof.
 19. A methodaccording to claim 15 wherein said adjunct ingredients are selected fromthe group consisting of builders, optical brighteners, soil releasepolymers, dye transfer agents, dispersents, enzymes, suds suppressers,dyes, perfumes, colorants, filler salts, hydrotropes, photoactivators,fluorescers, fabric conditioners, hydrolyzable surfactants,preservatives, anti-oxidants, chelants, stabilizers, anti-shrinkageagents, anti-wrinkle agents, germicides, fungicides, anti corrosionagents, and mixtures thereof.